Manufacturing method of semiconductor device having a high dielectric constant capacitor

Abstract: A manufacturing method of a semiconductor device forming a capacitor through an interlayer insulating layer on a semiconductor substrate on which an integrated circuit is provided. This manufacturing method comprise a step of forming an interlayer insulating layer which covers the capacitor and a passivation layer which covers the interconnections of the capacitor. According to the present invention, only the passivation layer above the top electrode of the capacitor or both the interlayer insulating layer and passivation layer is removed, the capacitor is heated and a second passivation layer by covering the upper part of the top electrode is formed.

Description: FIELD OF THE INVENTION The invention relates to a manufacturing method of semiconductor device having ferroelectric layer or high dielectric layer as capacitor dielectric layer. BACKGROUND OF THE INVENTION Recently, along with the trend of higher speed and lower power consumption of semiconductor device such as microcomputer and digital signal processor, electronic appliances for consumer use are more and more advanced in performance, while an electromagnetic interference which is an electromagnetic noise generated from these electronic appliances is posing a serious problem. Accordingly, not only in electronic appliances, but also in semiconductor devices used in them, measures against electromagnetic interference are demanded. The most effective measure against electromagnetic interference in the semiconductor device is to install a capacitor of a large capacitance between the bias line and ground line inside the semiconductor device, hitherto the capacitor was placed outside the semiconductor device. In addition, lately, nonvolatile random access memories in a simple construction having a capacitor, using a ferroelectric layer as capacitor dielectric layer, and dynamic random access memories having a capacitor using dielectric layer of high dielectric constant as storage capacitor have been developed. A conventional semiconductor device having capacitor is specifically described below. Fig. 1 is a partially sectional view of a representative semiconductor device. In Fig. 1, on a silicon substrate 1, an integrated circuit 6 represented by source/drain active areas 3, a gate oxide 4, and a gate electrode 5 is formed in a region enclosed by a field oxide area 2. Further on the silicon substrate 1, an insulating layer 7 is formed, and in a specific region on the insulating layer 7, a capacitor 11 consisting of a bottom electrode 8, a capacitor dielectric layer 9, and a top electrode 10 is formed. At least covering the capacitor 11, moreover, an interlayer insulating layer 12 is formed. There are also formed interconnections 14a connected to the source/drain active areas 3 through a first contact hole 13a, interconnection 14b connected to the bottom electrode 8 of the capacitor 11 through a second contact hole 13b, and interconnection 14c connected to the top electrode 10 of the capacitor 11 through a third contact hole 13c. Furthermore, a passivation layer 15 is formed in order to protect the interconnections 14a, 14b, 14c. A manufacturing method of the conventional semiconductor device having capacitor shown in Fig. 1 is explained below while referring to the flow chart of manufacturing process shown in Fig. 2, together with Fig. 1. First, at step (1), the integrated circuit 6 is formed on the silicon substrate 1. At step (2), an insulating layer 7 is formed on a silicon substrate 1. At step (3), a capacitor 11 is formed on the insulating layer 7. This capacitor 11 is formed by sequentially laminating a first conductive layer as bottom electrode 8, capacitor dielectric layer 9, and a second conductive layer as top electrode 10, and patterning respectively by etching. As the capacitor dielectric layer 9, a ferroelectric layer or high dielectric layer is used, and as bottom electrode 8 and top electrode 10, a two-layer composition consisting of platinum layer and titanium layer sequentially from the side contacting with the capacitor dielectric layer 9 is used. At step (4), an interlayer insulating layer 12 composed of PSG (phospho-silicate glass) is formed by CVD so that at least the capacitor 11 is covered. At step (5), a first contact hole 13a reaching the source/drain active areas 3 of the integrated circuit 6, a second contact hole 13b reaching the bottom electrode 8 of the capacitor 11, and a third contact hole 13c reaching the top electrode 10 of the capacitor 11 are formed. After forming interconnections 14a, 14b, 14c at step (6), a passivation layer 15 composed of silicon nitride layer or silicon oxynitride layer of high humidity resistance is formed by plasma CVD at step (7). However, in such conventional semiconductor device having capacitor, a PSG layer is used as interlayer insulating layer 12, and although the purpose of alleviating the stress to the capacitor 11 is achieved, the moisture generated when forming the PSG layer by CVD is absorbed by the PSG layer, and this moisture diffuses into the ferroelectric layer composing the capacitor dielectric layer, thereby lowering the electric resistance. This phenomenon gives rise to increase of leakage current of the capacitor 11 or decline of dielectric strength, which may induce dielectric breakdown of the capacitor dielectric layer 9. Yet, in such conventional semiconductor device having capacitor, as a passivation layer 15, silicon nitride layer or silicon oxynitride layer formed by plasma CVD is used, and although invasion of moisture from outside into the capacitor 11 may be prevented, activated hydrogen is generated in the layer forming process by plasma CVD, and this activated hydrogen may diffuse in the ferroelectric layer or high dielectric layer for composing the capacitor dielectric layer 9, which may induce increase of leakage current of the capacitor 11 or deterioration of electrical characteristic. Generally, the hydrogen atom content in the nitride layer formed by plasma CVD is as high as 10 22 atoms/cm 3 , and by heat treatment after layer forming, diffusion of hydrogen into the capacitor dielectric layer 9 is accelerated, and the characteristic of the capacitor 11 is further degenerated. Reference may be made to EP-A-0513894 (relative to which the invention is characterised), and to EP-A-0514546. SUMMARY OF THE INVENTION The invention is defined in the claims. In this constitution, the hydrogen alone or hydrogen compound contained in the capacitor dielectric layer can be easily released, so that increase of leakage current and a drop in dielectric strength of the capacitor can be prevented. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partially sectional view showing the structure of principal parts of a conventional semiconductor device having capacitor. Fig. 2 is a flow chart for explaining a conventional manufacturing method of semiconductor device having capacitor. Fig. 3 is a partially sectional view showing the structure of principal parts of a semiconductor device having capacitor in Example 1. Fig. 4 is a flow chart for explaining a manufacturing method of a semiconductor device having capacitor in Example 1. Fig. 5 is a diagram showing the temperature dependence of moisture release amount from PSG layer. Fig. 6 is a diagram showing the electrical reliability of the semiconductor device having capacitor in Example 1. Fig. 7, Fig. 8, Fig. 9, Fig. 10, and Fig. 11, are partially sectional views showing a manufacturing method of semiconductor device having capacitor of the invention, in which Fig. 7 is a diagram showing the state of forming a capacitor on an insulating layer of a semiconductor substrate in which an integrated circuit is formed, forming an interlayer insulating layer on the capacitor, and forming contact holes, Fig. 8 is a diagram showing the state of forming the interconnections, Fig. 9 is a diagram showing the state of forming a passivation layer to protect the interconnections, Fig. 10 is a diagram showing the state of forming a second passivation layer possessing an opening corresponding to the top electrode of the capacitor after forming interconnections, and Fig. 11 is a diagram showing the state of forming passivation layers in order to protect the interconnections. Fig. 12 is a diagram showing the result of measuring the leakage current after each step of a semiconductor device having capacitor manufactured according to the invention. Fig. 13 is a diagram showing the electircal reliability of semi conductor device having capacitor manufactured according to the invention. DESCRIPTION OF THE PREFERRED EMBODIMENT Before to describe the manufacturing process of the invention explained in Fig. 7, Fig. 8, Fig. 9, Fig. 10 and Fig. 11, we will describe the semiconductor device of Example 1 shown in Fig. 3 as well as the manufacturing method thereof shown in Fig. 4. Example 1 In a semiconductor device of the invention shown in Fig. 3, an isolation oxide layer 32 is formed on a silicon substrate 31, and an integrated circuit 36 represented by a transistor composed of a diffusion region 33, a gate insulating layer 34, and a gate electrode 35 is formed in a region enclosed by the isolation oxide layer 32. On the silicon substrate 31, an insulating layer 37 composed of silicon oxide layer is formed, and a capacitor 41 comprising a bottom electrode 38 of platinum layer and titanium layer, a capacitor dielectric layer 39 composed of ferroelectric layer or high dielectric layer, and a top electrode 40 composed of platinum layer and titanium layer is formed on the insulating layer 37. Covering this capacitor 41, an interlayer insulating layer 42 composed of a PSG layer having the moisture content of 0.5g or less per 1 cm 3 is formed. In the conventional semiconductor device having capacitor, the moisture content of the interlayer insulating layer was 0.9g or more per 1 cm 3 . Above the integrated circuit 36, a first contact hole 43a reaching a diffusion region 33 is formed in the insulating layer 37 and interlayer insulating layer 42, and above the capacitor 41, a contact hole 43b reaching the bottom electrode 38 and a third contact hole 43c reaching the top electrode 40 are formed in the interlayer insulating layer 42. Through the first contact hole 43a, an interconnection 44a composed of aluminum layer or aluminum alloy layer connected to the diffusion region 33 is formed, and through the second and third contact holes 43b, 43c, interconnections 44b, 44c composed of aluminum layer or aluminum alloy layer connected to the bottom electrode 38 and top electrode 40 are formed. To protect these interconnections 44a, 44b, 44c, a passivation layer 45 composed of silicon nitride layer or silicon oxynitride layer is formed. According to such constitution of Example 1, in the interlayer insulating layer 42, the moisture content is controlled under 0.5g per 1 cm 3 , and if heated in the subsequent steps, diffusion of moisture into the capacitor dielectric layer 39 can be prevented, thereby preventing increase of leakage current and a drop in dielectric strength of the capacitor 41, so that a semiconductor device having the capacitor 41 hardly inducing trouble due to dielectric breakdown as compared with the prior art may be realized. A manufacturing method of such semiconductor device is explained below while referring to the flow chart of manufacturing method shown in Fig. 4, together with Fig. 3. First, at step (1), an integrated circuit 36 and others are formed on a silicon substrate 31. At step (2), an insulating layer 37 is formed on the silicon substrate 31. At step (3), a capacitor 41 is formed on the insulating layer 37. This capacitor 41 is formed by sequentially laminating a first conductive layer as bottom electrode 38, a capacitor dielectric layer 39, and a second conductive layer as top electrode 40, and patterning respectively by etching. As the capacitor dielectric layer 39, a ferroelectric layer or high dielectric layer is used, and as the bottom electrode 38 and top electrode 40, a two-layer composition consisting of a platinum layer and a titanium layer sequentially from the side contacting with the capacitor dielectric layer 39 is used. At step (4), the capacitor 41 is heated to enhance and stabilize the characteristic of the capacitor dielectric layer 39. At step (5), at least covering the capacitor 41 by CVD or the like, an interlayer insulating layer 42 composed of PSG layer (photo-silicate glass layer) is formed, and at step (6), the interlayer insulating layer 42 is heated in a nitrogen atmosphere, and the moisture contained in the interlayer insulating layer 42 is removed to not more than 0.5g per 1 cm 3 of the interlayer insulating layer 42. At step (7), a first contact hole 43a reaching the diffusion region 33 of the integrated circuit 36, and second and third contact holes 43b and 43c reaching the bottom electrode 38 and top electrode 40 of the capacitor 41 are formed. At step (8), interconnections 44a, 44b, 44c are formed, and at step (9), a passivation layer 45 composed of silicon nitride layer or silicon oxynitride layer high in humidity resistance is formed by plasma CVD. In the foregoing constitution and manufacturing method, the PSG layer is formed as interlayer insulating layer 42 by CVD, and the moisture is removed from the PSG layer in a subsequent heat treatment process, but it is not limited to this, and for example, a silicon oxide layer may be formed in a condition of high temperature and reduced pressure, and heat treatment may be omitted. In the manufacturing method described above, heat treatment of the interlayer insulating layer 42 at step (6) in Fig. 4 is conducted in nitrogen gas, but it may be also done in inert gas such as helium and argon, or in vacuum. Results of measurement of moisture adsorption of PSG layer formed by CVD are explained below by reference to Fig. 5. The abscissa in Fig. 5 denotes the temperature, and the ordinate represents the amount of moisture released at the corresponding temperature, and their relation corresponds to the intensity of moisture adsorption. As shown in Fig. 5, the peak temperature of the adsorbed moisture releasing from the PSG layer is 300 to 350°C in a first peak, and 450 to 530°C in a second peak. The moisture corresponding to the second peak is adsorbed to the PSG layer with a sufficiently strong adsorption, and it seems to hardly affect the reliability in normal use. By contrast, the first peak drags its foot down to the low temperature side, and water is released in a condition relatively close to operating temperature, and it seems to induce deterioration of the capacitor dielectric layer 39. The inventors discovered it preferable to heat at 350°C or higher in order to release the adsorbed water corresponding to the first peak in Fig. 4 right after forming the layer by CVD. Furthermore, as the interlayer insulating layer 42, heat treatment of silicon oxide layer containing phosphorus by 6 wt.% or less is found to be preferred also for lessening the stress applied to the capacitor 41. Besides, the above heat treatment is performed at a not higher temperature than temperature giving rise to deterioration of a characteristic of the integrated circuit. The deterioration generally occurs at about 900 °C. It is preferable to heat at about 850°C or lower. The result of evaluation of reliability of the capacitor 41 manufactured in this embodiment is shown in Fig. 6. As the capacitor dielectric layer 39, barium strontium titanate was used. The abscissa denotes the inverse number of electric field applied to the capacitor 41, and the ordinate represents the time until the leakage current reaches a specific value. Line (a) shows the leakage current while applying a voltage to the capacitor 41 manufactured by a conventional method, and the moisture content of the PSG layer used as interlayer insulating layer 42 was 0.93 g/cm 3 . Line (b) relates to the result of the capacitor 41 manufactured in the embodiment, and the moisture content of the PSG layer as interlayer insulating layer 42 was 0.45 g/cm 3 . By comparing these lines, it has been proved that the capacitor 41 of the embodiment lower in the moisture content of the interlayer insulating layer 42 is superior by far as compared with the conventional example. Incidentally, the moisture content in the PSG layer may be 0.5 g/cm 3 or less. In the example, after forming and heating the interlayer insulating layer 42, the contact holes 43a, 43b, 43c are formed, but the sequence of heat treatment may be changed in the order of formation of interlayer insulating layer 42, formation of contact holes 43a, 43b, 43c, and heat treatment. In such a case, the contact holes 43a, 43b, 43c serve as vent holes, and moisture adsorbed on the capacitor 41 is released easily. In this example, the interlayer insulating layer 42 is heated once, but the heat treatment may be divided in plural steps. For example, a first heat treatment may be given after forming the interlayer insulating layer 42, and a second heat treatment after forming the contact holes 43a, 43b, 43c. In this case, the heat treatment condition may be varied between the first and second heat treatment processes. Embodiment of the invention The manufacturing process of the invention, which is now explained with references to Fig. 7, Fig. 8, Fig. 9, Fig. 10 and Fig. 11 is the manufacturing process of the semiconductor device having a second interlayer insulating layer 59 attached to Example 1. First, as shown in Fig. 7, an insulating layer 37 is formed on a silicon substrate 31 in which an integrated circuit 36 is fabricated, and a capacitor 41 is formed on the insulating layer 37, and an interlayer insulating layer 46 such as silicon oxide layer is formed to cover the capacitor 41, and first contact hole 43a, second contact hole 43b, and third contact hole 43c are formed. As the bottom electrode 38 and top electrode 40 of the capacitor 41, a platinum layer having a titanium layer placed on the other side the capacitor is used. Next, as shown in Fig. 8, after forming interconnections 44a, 44b, 44c, a second interlayer insulating layer 59 composed of silicon nitride layer or silicon oxynitride layer is formed on the entire surface by plasma CVD or the like as shown n Fig. 9. Next, as shown in Fig. 10, opening 60 corresponding to the capacitor 41 is formed in the second interlayer insulating layer 59 on the top of the capacitor 41. In this state, in order to take hydrogen or hydrogen compound away from the capacitor dielectric layer 39, heat treatment is applied by using nitrogen, argon, or their mixed gas, or in vacuum. Successive to this heat treatment, in order to supply oxygen into the capacitor dielectric layer 39, heat treatment is applied by using oxygen, or mixed gas of oxygen with ni trogen, or with argon or the like. Then, as shown in Fig. 11, a passivation layer 55 composed of silicon nitride layer or organic insulating layer is formed. According to such constitution, after removing the second interlayer insulating layer 59 on the capacitor 41, heat treatment of the capacitor 41 (that is, heat treatment of capacitor dielectric layer 39) is effected in nitrogen, argon, or their mixed gas, or in vacuum, at 400°C or less, thereby easily releasing hydrogen or hydrogen compound, which causes deterioration of ferroelectric layer or high dielectric layer. By successively performing heat treatment, using oxygen, or mixed gas of oxygen with nitrogen, argon, or the like, at 400°C or less, the vacancy of oxygen greatly contributing to the electric conductivity of ferroelectric layer or high dielectric layer may be filled up. Results of measurement of leakage current and results of dielectric breakdown characteristic of capacitor dielectric layer 39 before and after forming silicon nitride layer on the capacitor 41 and after heat treatment are explained below while referring to Fig. 12 and Fig. 13. Fig. 12 shows the result of measurement of leakage current when barium strontium titanate layer is used as the capacitor dielectric layer 39, in which after the silicon nitride layer is formed by plasma CVD as the second interlayer insulating layer 59, the leakage current has taken a figure up about two places, but by heat treatment, the leakage current takes a figure down two or three places, returning to the state before forming the silicon nitride layer. Fig. 13 shows the relation between the inverse number of the electric field intensity E (MV/cm) applied to the capacitor 41 and the lifetime, in which a broken line refers to the lifetime when a silicon nitride layer is formed as the second interlayer insulating layer 59 and heat treatment is not given, and a solid line shows the lifetime when a silicon nitride layer is formed as the second interlayer insulating layer 59 and heat treatment is given. In any case, the silicon nitride layer is formed by plasma CVD. In this way, by heating after forming the silicon nitride layer or silicon oxynitride layer as the second interlayer insulating layer 59 by plasma CVD method, the lifetime to dielectric breakdown at high temperature and in high electric field deteriorating in the plasma CVD process can be recovered to a sufficiently practical level. In the manufacturing method of semiconductor device herein, an example of heating the capacitor 41 before and after forming the interconnections 44a, 44b, 44c has been explained, but similar effects may be obtained by other method, for example, by forming first, second and third contact holes 43a, 43b, 43c shown in Fig. 7, heating in nitrogen, argon, or their mixed gas or in vacuum in order to take hydrogen or hydrogen compound away from the capacitor dielectric layer 39, and successively heating by using oxygen, or mixed gas of oxygen with nitrogen, argon or the like in order to supply oxygen into the capacitor dielectric layer 39. In this case, as the second interlayer insulating layer 59, it is preferred to use a layer formed in other method than plasma CVD. In this case, the heat treatment before and after forming the interconnections 44a, 44b, 44c required in the above manufacturing method is not necessary. In this embodiment, an example of forming an opening 60 corresponding to the capacitor 41 in the second interlayer insulating layer 59 is explained, but the opening 60 may be also provided in correspondence with the top electrode 40 of the capacitor 41, and it is possible to release the hydrogen or hydrogen compound in the capacitor dielectric layer 39 in the heat treatment process.

Claims: A manufacturing method of a semiconductor device comprising the following sequence of steps: forming on an insulating layer (37) of a semiconductor substrate in which an integrated circuit (36) is fabricated, a capacitor (41) comprising a bottom electrode (38) composed of a conductive layer, a capacitor dielectric layer (39) composed of one of a ferroelectric layer and a high dielectric permittivity layer formed on the bottom electrode, and a top electrode (4) composed of a conductive layer formed on the capacitor dielectric layer (39), forming a first interlayer insulating layer (46) by covering the entire semiconductor device including said capacitor, forming contact holes (43a, 43b, 43c) reaching the integrated circuit, top electrode and bottom electrode of the capacitor, through the insulating layer (37) and the first interlayer insulating layer (46), forming interconnections (44a, 44b, 44c) to be electrically connected with the integrated circuit and capacitor through the contact holes, forming a second interlayer insulating layer (59) all over the semiconductor device covering the interconnections, characterized by , in sequence, selectively removing said second interlayer insulating layer (59) at the location of said capacitor, heat treating said capacitor in order to take hydrogen or hydrogen compound away from the capacitor dielectric layer (39), and depositing a passivation layer (55) over all the semiconductor device including by covering again the upper part of the top electrode. A manufacturing method of semiconductor device of claim 1, wherein the heat treatment step of the capacitor consists of a first step of heating in inert gas or in a vacuum, and a second step of heating in gas containing oxygen. A manufacturing method of semiconductor device of claim 1 or 2, wherein a heat treatment of the capacitor (41) is provided before or after forming the interconnections (44a, 44b, 44c). A manufacturing method of semiconductor device of claim 1, 2 or 3, wherein said heat treatment step comprises heating at not more than 400°C.

Inventors: ARITA KOJI, FUJII EIJI, INOUE ATSUO, MATSUDA AKIHIRO, MATSUURA TAKETOSHI, NAGANO YOSHIHISA, NASU TORU, OTSUKI TATSUO, SHIMADA YASUHIRO, UEMOTO YASUHIRO, ARITA, KOJI, FUJII, EIJI, INOUE, ATSUO, MATSUDA, AKIHIRO, MATSUURA, TAKETOSHI, NAGANO, YOSHIHISA, NASU, TORU, OTSUKI, TATSUO, SHIMADA, YASUHIRO, UEMOTO, YASUHIRO
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1994
Main classification: H01L27
IPC codes: H01L21, H01L27